WO2022097493A1 - 成形材料および成形品 - Google Patents

成形材料および成形品 Download PDF

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Publication number
WO2022097493A1
WO2022097493A1 PCT/JP2021/038942 JP2021038942W WO2022097493A1 WO 2022097493 A1 WO2022097493 A1 WO 2022097493A1 JP 2021038942 W JP2021038942 W JP 2021038942W WO 2022097493 A1 WO2022097493 A1 WO 2022097493A1
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WIPO (PCT)
Prior art keywords
polyphenylene sulfide
molding material
sulfide
resin
reinforcing fiber
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PCT/JP2021/038942
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English (en)
French (fr)
Japanese (ja)
Inventor
平田慎
鈴木貴文
濱口美都繁
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to EP21889046.5A priority Critical patent/EP4242259A4/en
Priority to US18/034,454 priority patent/US20240017444A1/en
Priority to CN202180072578.6A priority patent/CN116419947A/zh
Priority to JP2021565816A priority patent/JPWO2022097493A1/ja
Publication of WO2022097493A1 publication Critical patent/WO2022097493A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

Definitions

  • the present invention relates to a molding material containing a reinforcing fiber bundle and polyphenylene sulfide, and a molded product containing reinforcing fibers and polyphenylene sulfide.
  • thermoplastic prepregs, yarns, and glass mats are known as molding materials using a continuous reinforcing fiber bundle and a thermoplastic resin as a matrix.
  • a molding material is easy to mold by taking advantage of the characteristics of a thermoplastic resin, does not require a storage load like a thermosetting resin, and the obtained molded product has high toughness and is recyclable. It has the characteristic of being excellent.
  • the molding material processed into pellets can be applied to molding methods having excellent economic efficiency and productivity such as injection molding and stamping molding, and is useful as an industrial material.
  • Patent Documents 1 and 2 disclose that a molded product having high mechanical properties can be obtained by injection molding a molding material composed of a continuous reinforcing fiber bundle and a polyphenylene sulfide resin.
  • Patent Document 3 discloses that polyarylene sulfide containing a paraarylene sulfide unit, a metaarylene sulfide unit and a filler improves adhesiveness to an epoxy resin while maintaining heat resistance and mechanical properties. ..
  • a molding material containing a bundle of reinforcing fibers which has good moldability, dimensional accuracy, and appearance characteristics even when molded into a small size, thin wall, or a complicated shape, has not yet been found.
  • the subject of the present invention has been made in view of the above circumstances, and more specifically, by reducing the generation of gas during the molding process and suppressing the surface roughness of the molded product, the molded product It is an object of the present invention to provide a molding material capable of achieving both excellent surface smoothness and mechanical properties.
  • the polyphenylene sulfide (B) contains a paraphenylene sulfide unit and a metaphenylene sulfide unit, and the content of the metaphenylene sulfide unit is 7 mol% or more with respect to the total amount of the paraphenylene sulfide unit and the metaphenylene sulfide unit.
  • [3] The molding material according to [1] or [2], wherein the molding material is a long fiber pellet.
  • the reinforcing fiber bundles (A) are arranged in parallel in parallel with the axial direction of the molding material, and the length of the reinforcing fiber bundles (A) is substantially the same as the length of the molding material.
  • [5] The molding material according to any one of [1] to [4], wherein the temperature-decreasing crystallization temperature of the polyphenylene sulfide (B) is 190 ° C. or lower.
  • the polyphenylene sulfide contains a paraphenylene sulfide unit and a metaphenylene sulfide unit, and the content of the metaphenylene sulfide unit is 7 mol% or more with respect to the total amount of the paraphenylene sulfide unit and the metaphenylene sulfide unit.
  • the molded product according to any one of [10] to [12].
  • polyphenylene sulfide according to any one of [10] to [13], which comprises a homopolyphenylene sulfide composed of only paraphenylene sulfide units and a copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units. Molded product.
  • the present invention it is possible to reduce the generation of gas derived from the reinforcing fiber bundle and the sizing agent during the molding process, and it is possible to suppress the surface roughness of the molded product due to the gas, so that the surface smoothness and mechanical properties of the molded product can be improved.
  • a compatible molding material can be obtained.
  • the molding material of the present invention can suppress the generation of gas derived from the reinforcing fiber bundle and the sizing agent during the molding process, and the reinforcing fibers are well dispersed in the molded product during injection molding. Because it is possible to easily manufacture molded products with excellent mechanical properties, it is not limited to molding methods such as injection molding, transfer molding, blow molding, insert molding, etc., but also a wide range of molding methods such as plunger molding, press molding, stamping molding, etc. It can also be applied to molding methods.
  • Molded products obtained by molding the molding material of the present invention include thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, automobile parts such as pedals, silicon wafer carriers, and IC chip trays. , Semiconductor / liquid crystal manufacturing equipment parts such as electrolytic condenser trays and insulating films, compressor parts such as pumps, valves and seals, industrial machine parts such as aircraft cabin interior parts, medical equipment parts such as sterilization equipment, columns and pipes, and food products. Beverage manufacturing equipment parts can be mentioned. Further, the molding material of the present invention can relatively easily obtain a thin-walled molded product having a thickness of 0.5 to 2 mm.
  • Such thin-walled molding is required, for example, as represented by a housing used for a personal computer, a mobile phone, etc., and a keyboard support which is a member for supporting the keyboard inside the personal computer.
  • Examples include members for electric and electronic devices. In such a member for electric / electronic equipment, when carbon fiber having conductivity is used for the reinforcing fiber, electromagnetic wave shielding property is imparted, which is suitable.
  • FIG. 1 It is a schematic diagram which shows still another example of the shape of the cross section in the direction orthogonal to the axis of a preferred embodiment of the molding material of this invention. It is an internal perspective perspective view (schematic view) of a general long fiber pellet. It is an internal perspective perspective view (schematic diagram) of a general short fiber pellet.
  • the molding material of the present invention contains a reinforcing fiber bundle (A) and polyphenylene sulfide (B).
  • A reinforcing fiber bundle
  • B polyphenylene sulfide
  • the molding material of the present invention preferably contains polyphenylene sulfide (B) and a composite, and the composite is preferably composed of a reinforcing fiber bundle (A) and a resin (C).
  • the resin (C) is preferably one or more resins selected from the group consisting of epoxy resins, phenol resins and terpene resins.
  • the composite is coated with polyphenylene sulfide (B). That is, the composite composed of the reinforcing fiber bundle (A) and the resin (C) (impregnated resin) selected from the group consisting of the epoxy resin, the phenol resin and the terpene resin is coated with the polyphenylene sulfide (B). Is preferable.
  • the handleability of the molding material is improved.
  • the molding material of the present invention is kneaded by, for example, injection molding to obtain a final molded product. From the viewpoint of handleability of the molding material, the complex and the polyphenylene sulfide resin are not separated until molding is performed, and the above-mentioned form (the form in which the complex is coated with polyphenylene sulfide (B)) is maintained. It is important to be.
  • the molding material is the reinforcing fiber bundle and the polyphenylene sulfide resin during material transfer in the molding process.
  • the complex is filled with a resin (C) (hereinafter, the resin (C) may be referred to as an "impregnated resin") between each single fiber of the reinforcing fiber bundle (A).
  • the resin (C) is impregnated between the single fibers of the reinforcing fiber bundle (A). That is, it is a complex in which reinforcing fibers are dispersed like islands in the sea of impregnated resin.
  • the reinforcing fiber bundle (A) is completely impregnated with the impregnated resin, but the complex composed of the reinforcing fiber bundle (A) and the impregnated resin may have some voids.
  • the void ratio is preferably in the range of 0 to 40% or less. More preferably, it is 0 to 20% or less. When the void ratio is in the range, the effect of impregnation and promotion of fiber dispersion is excellent.
  • the void ratio is measured by measuring the portion of the complex by the ASTM 2734 (1997) test method.
  • the form of the coating is not particularly limited, and examples thereof include a form in which polyphenylene sulfide (B) covers a part or all of the periphery of the strand-shaped complex.
  • polyphenylene sulfide (B) covers a part or all of the periphery of the strand-shaped complex.
  • All around the strand-shaped complex is coated with polyphenylene sulfide (B).
  • the state of the boundary between the complex and the polyphenylene sulfide (B) is not particularly limited, but is partially near the boundary between the complex and the polyphenylene sulfide (B).
  • Polyphenylene sulfide (B) may enter a part of the complex and be in a state of being compatible with the impregnated resin in the complex, or a state of being impregnated in the reinforcing fiber bundle (A). preferable.
  • the coated polyphenylene sulfide (B) is less likely to be peeled off from the complex, a molding material with good handleability can be obtained, and a stable feed is achieved during molding, so that gas generation can be reduced. Uniform plasticization can be achieved and excellent fluidity can be developed.
  • the molding material of the present invention is preferably in the form of pellets and is preferably long fiber pellets.
  • the long fiber pellet refers to a resin material containing reinforcing fibers having substantially the same length as the pellet length in substantially the same direction.
  • long fiber pellets have a longer fiber length in a molded product after molding than short fiber pellets, and therefore exhibit excellent mechanical properties.
  • long fiber pellets tend to be significantly inferior in formability (fluidity).
  • polyphenylene sulfide is used as the thermoplastic resin, the tendency is remarkable because polyphenylene sulfide has a high molding temperature and a high crystallization rate.
  • the molding temperature is raised in order to improve the moldability (fluidity)
  • the amount of gas derived from the reinforcing fiber bundle and the sizing agent during the molding process increases, and the appearance characteristics (surface smoothness) of the molded product are improved. descend.
  • the molding material is a long fiber pellet and the thermoplastic resin used is polyphenylene sulfide, it is low by adopting the embodiment of the present invention, that is, by using polyphenylene sulfide having a melting point of 270 ° C. or lower.
  • the molding process can be performed at the molding temperature. As a result, while maintaining excellent mechanical properties, it is possible to greatly suppress the generation of gas derived from the reinforcing fiber bundle and the sizing agent during the molding process, and it is possible to significantly improve the moldability (fluidity). can.
  • the short fiber pellet refers to a resin material in which reinforcing fibers are randomly dispersed in a thermoplastic resin.
  • FIG. 6 is an internal permeation perspective view of the long fiber pellet (schematic diagram) (in the figure, reference numeral 1 indicates a reinforcing fiber bundle (A), reference numeral 2 indicates a polyphenylene sulfide (B)), and FIG. 7 shows the inside of the short fiber pellet.
  • a transmission perspective view (schematic diagram) is shown (in the figure, reference numeral 2 indicates polyphenylene sulfide (B), and reference numeral 3 indicates reinforcing fibers).
  • the long fiber pellets can be produced by a known method.
  • the reinforcing fiber bundles (A) are arranged in parallel in parallel with the axial direction of the molding material (preferably pellets), and the length of the reinforcing fiber bundle (A) is substantially the length of the molding material. It is preferable that they are the same.
  • parallel parallel means a state in which the axis of the long axis of the reinforcing fiber bundle (A) and the axis of the long axis of the molding material are oriented in the same direction, and the angle between the axes.
  • the deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less.
  • substantially the same length means that, for example, in a pellet-shaped molding material, the reinforcing fiber bundle (A) is cut in the middle of the inside of the pellet, or the reinforcing fiber bundle (A) significantly shorter than the total length of the pellet is substantially the same. It is not included in the target.
  • the amount of the reinforcing fiber bundle (A) shorter than the total length of the pellet is not specified, but when the content of the reinforcing fiber having a length of 50% or less of the total length of the pellet is 30% by mass or less. , It is evaluated that the reinforcing fiber bundle (A) significantly shorter than the total length of the pellet is not substantially contained.
  • the content of the reinforcing fiber having a length of 50% or less of the total length of the pellet is preferably 20% by mass or less.
  • the total length of the pellet is the length of the pellet in the direction parallel to the orientation direction of the reinforcing fibers in the pellet. Since the reinforcing fiber bundle (A) has substantially the same length as the molding material, the reinforcing fiber length in the molded product can be lengthened, and excellent mechanical properties can be obtained.
  • the length of the molding material there is no particular limitation on the length of the molding material, and it can be used continuously or as long as it is, depending on the molding method.
  • a thermoplastic yarn prepreg it can be wound around a mandrel while being heated to obtain a roll-shaped molded product.
  • the molding material is preferably 1 to 50 mm long fiber pellets. It is more preferably 3 to 20 mm, and most preferably 5 to 10 mm.
  • FIGS. 3 to 5 schematically show the shape of the cross section in the direction orthogonal to the axial center of the molding material of the present invention. It is a representation of the target.
  • the shape of the cross section of the molding material is not limited to that shown in the figure, but preferably, as shown in FIG. 1, which is a cross section in the axial direction, the reinforcing fiber bundle (A) serves as a core material and the polyphenylene sulfide (B). It is preferable that the components are sandwiched between layers.
  • the reinforcing fiber bundle (A) has a core structure and the polyphenylene sulfide (B) has a sheath structure.
  • the molding material preferably has a core-sheath structure in which the polyphenylene sulfide (B) covers the periphery of the reinforcing fiber bundle (A).
  • the molding material may contain a complex composed of the reinforcing fiber bundle (A) and the resin (C), the "reinforced fiber bundle (A)” is read as “complex”, and the "composite” in FIGS. 1 to 6 is used. 1: “Reinforcing fiber bundle (A)” is read as "complex”.
  • polyphenylene sulfide (B) can be kneaded into a complex composed of a reinforcing fiber bundle (A) and an impregnated resin by a method such as injection molding or press molding to obtain a final molding material. From the viewpoint of handleability of the molding material, it is preferable that the complex and the polyphenylene sulfide (B) are not separated until molding is performed, and the polyphenylene sulfide (B) keeps the form of covering the complex. Since the impregnated resin has a low molecular weight, it is often a solid that is relatively brittle and easily crushed. Therefore, polyphenylene sulfide (B) is arranged so as to protect the complex so that the impregnated resin is not crushed and scattered due to transportation of the material until molding, impact during handling, rubbing, etc. Is desirable.
  • the reinforcing fiber bundle (A) in the present invention refers to a state in which single fibers are arranged in one direction.
  • Examples of the form of the reinforcing fiber bundle (A) include a unidirectional fiber bundle, a bidirectional fiber bundle, and a multidirectional fiber bundle, but the unidirectional fiber bundle is unidirectional from the viewpoint of productivity in the process of manufacturing the molding material.
  • Fiber bundles can be used more preferably.
  • the reinforcing fiber bundle (A) the larger the number of single yarns of the reinforcing fibers is, the more economically advantageous it is. Therefore, the number of single fibers is preferably 10,000 or more.
  • the type of the reinforcing fiber constituting the reinforcing fiber bundle (A) is not particularly limited, and for example, carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, natural fiber, mineral fiber. Etc. can be used, and these may be used alone or in combination of two or more. Among them, PAN (polyacrylic nitrile) -based, pitch-based, rayon-based and other carbon fibers are preferably used from the viewpoint of obtaining a molded product having a light weight, high strength and a high elastic modulus.
  • reinforcing fibers having a tensile strength of 4,000 MPa or more are preferable, and more preferably 5,000 MPa or more.
  • reinforcing fibers having a tensile elastic modulus of 200 GPa or more are preferable, and more preferably 400 GPa or more.
  • a reinforcing fiber having an elastic modulus of 400 GPa or more, which is difficult to maintain a long fiber length, is preferable because the effect of the molding material of the present invention described later can be more exhibited.
  • glass fiber can be preferably used from the viewpoint of enhancing the economic efficiency of the obtained molded product, and it is particularly preferable to use carbon fiber and glass fiber in combination from the viewpoint of the balance between mechanical properties and economic efficiency.
  • aramid fibers can be preferably used from the viewpoint of enhancing the impact absorption and shapeability of the obtained molded product, and it is particularly preferable to use carbon fibers and aramid fibers in combination from the viewpoint of the balance between mechanical properties and impact absorption.
  • reinforced fibers coated with a metal such as nickel, copper or ytterbium, or pitch-based carbon fibers can also be used.
  • a sizing agent is attached to the reinforcing fiber bundle (A).
  • the type of the sizing agent is not particularly limited, but one or more kinds of sizing agents such as epoxy resin, urethane resin, acrylic resin and various thermoplastic resins can be used in combination.
  • the reinforcing fiber bundle (A) is preferably 1% by mass or more and 50% by mass or less with respect to the total amount (100% by mass) of the molding material. More preferably, it is 10% by mass or more and 30% by mass or less. If the content of the reinforcing fiber bundle (A) is less than 1% by mass, the mechanical properties of the obtained molded product may be insufficient, and if it exceeds 50% by mass, it is derived from the reinforcing fiber or the sizing agent adhering to the reinforcing fiber. The amount of gas generated may increase.
  • the melting point of polyphenylene sulfide (B) in the present invention is 270 ° C. or lower.
  • the melting point of polyphenylene sulfide (B) can be determined from the temperature of the apex of the melting peak in the differential scanning calorimetry. When two or more polyphenylene sulfides are used and the mixture thereof exhibits a single melting peak, the melting point can be determined from the apex of the melting peak. On the other hand, when two or more kinds of polyphenylene sulfides are used and a plurality of melting peaks are observed, the melting point is obtained from the apex of each melting peak.
  • the molding temperature can be lowered and the generation of gas generated during molding can be suppressed. It can also improve economic efficiency.
  • the molding material contains an impregnated resin or when a sizing agent is attached to the reinforcing fiber, decomposition of the impregnating resin or the sizing agent during the molding process can be suppressed, so that the impregnation has relatively low heat resistance. It becomes possible to select a resin or a sizing agent. That is, it is possible to increase the degree of freedom in designing the impregnated resin and the sizing agent and the degree of freedom in selecting the impregnating resin and the sizing agent.
  • the melting point of polyphenylene sulfide (B) is more preferably 260 ° C. or lower. Since the melting point of the polyphenylene sulfide (B) is 270 ° C. or lower, the molding temperature can be lowered, and the decomposition gas at the time of molding is suppressed and the economy is excellent. In particular, when the molding material contains an impregnated resin or when a sizing agent is attached to the reinforcing fiber, the decomposition of the impregnating resin or the sizing agent can be suppressed, and the degree of freedom of the impregnating resin or the sizing agent should be increased. Is possible. Further, from the viewpoint of heat resistance, the melting point of polyphenylene sulfide (B) is preferably 240 ° C. or higher. The melting point of polyphenylene sulfide (B) is measured as follows.
  • the sample is heated at a heating rate of 20 ° C./min from 40 ° C. to 340 ° C. with a differential scanning calorimeter.
  • the temperature of the sample is lowered from 340 ° C. to 40 ° C. at a temperature lowering rate of 20 ° C./min.
  • the temperature of the sample is raised again from 40 ° C. to 340 ° C. at a heating rate of 20 ° C./min.
  • the apex of the melting peak observed in the heating process of [3] above is defined as the melting point.
  • the method for lowering the melting point of polyphenylene sulfide (B) to 270 ° C. or lower is not particularly limited, but metaphenylene sulfide and / or orthophenylene sulfide is copolymerized with polyphenylene sulfide mainly formed of a paraphenylene sulfide skeleton.
  • metaphenylene sulfide and / or orthophenylene sulfide is copolymerized with polyphenylene sulfide mainly formed of a paraphenylene sulfide skeleton.
  • Examples thereof include a method of block-copolymerizing another polymer at the terminal of polyphenylene sulfide, and a method of reducing molecular motility by oxidatively cross-linking polyphenylene sulfide.
  • Etherketone polyether ether ketone, polythioether ketone, polytetrafluoroethylene, polyorganosiloxane, thermoplastic polyurethane resin, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, polyacrylic acid ester, polymethacrylic Examples thereof include polyolefins such as acid esters, poly1-butene, poly1-pentene, polymethylpentene, and ethylene / ⁇ -olefin copolymers.
  • the polyphenylene sulfide (B) is preferably a polyphenylene sulfide obtained by copolymerizing paraphenylene sulfide and metaphenylene sulfide. That is, in the present invention, the polyphenylene sulfide (B) preferably contains a paraphenylene sulfide unit and a metaphenylene sulfide unit. In the present invention, the content of the metaphenylene sulfide unit is preferably 7 mol% or more with respect to the total amount of the paraphenylene sulfide unit and the metaphenylene sulfide unit.
  • the content of the metaphenylene sulfide unit is more preferably 8 mol% or more, further preferably 10 mol% or more, and particularly preferably 10.5 mol% or more.
  • the melting point of polyphenylene sulfide can be lowered, the crystallization rate of polyphenylene sulfide (B) is lowered, and the fluidity is improved.
  • the content of the metaphenylene sulfide unit is less than 7 mol%, it may not be possible to sufficiently lower the melting point of the polyphenylene sulfide.
  • the upper limit of the content of the metaphenylene sulfide unit of polyphenylene sulfide is not particularly limited, but is preferably 20 mol% or less, and more preferably 14 mol% or less.
  • the content of the metaphenylene sulfide unit is 20 mol% or less, the mechanical properties can be achieved, the demolding property at the time of molding is improved, and the molding cycle property is also good.
  • it is 14 mol% or less, in addition to being able to achieve both excellent fluidity and mechanical properties, the moldability during molding is improved, and the molding cycle property can be improved.
  • the metaphenylene sulfide unit is larger than 20 mol%, it may not be preferable because the inherent heat aging resistance and chemical resistance of polyphenylene sulfide are lowered.
  • the molding material is in the form of covering a part or all of the periphery of the strand-shaped composite with polyphenylene sulfide (B), if the content of the metaphenylene sulfide unit is 7 mol% or more, the composite is coated. Crystallization of polyphenylene sulfide (B) is suppressed, polyphenylene sulfide (B) is less likely to break, and a molding material with excellent handleability can be obtained.
  • the variation in the mechanical properties of the molded product can be suppressed, the surface smoothness can be improved, the decrease in the fluidity of the molded material can be suppressed, and the fluidity can be suppressed. Can be improved.
  • the content of the metaphenylene sulfide unit is 7 mol% or more, the polyphenylene sulfide is used.
  • (B) is preferable because it is hard to break.
  • the shear stress applied to the reinforcing fibers during kneading or molding can be reduced, and the reinforcing fiber bundle (A) of the molded product can be reduced.
  • the fiber length can be maintained for a long time.
  • it is preferable because the effect of the molding material of the present invention can be more exhibited on the reinforcing fiber having an elastic modulus of 350 GPa or more, which is difficult to maintain the fiber length for a long time.
  • the metaphenylene sulfide unit of polyphenylene sulfide (B) is measured using a Fourier transform infrared spectroscope (hereinafter, abbreviated as FT-IR). Specifically, the content of the metaphenylene sulfide unit is calculated from the size of the absorption peak of 780 cm -1 , which is the absorption peak of the metaphenylene sulfide unit.
  • FT-IR Fourier transform infrared spectroscope
  • the temperature-decreasing crystallization temperature of polyphenylene sulfide (B) is preferably 190 ° C. or lower. More preferably, it is 170 ° C. or lower.
  • the temperature-decreasing crystallization temperature of the polyphenylene sulfide (B) is 190 ° C. or lower, the crystallization rate is slowed down and the fluidity during molding is excellent.
  • the lower limit of the temperature-decreasing crystallization temperature of polyphenylene sulfide (B) is preferably 140 ° C.
  • thermodecreasing crystallization temperature of polyphenylene sulfide (B) To measure the temperature-decreasing crystallization temperature of polyphenylene sulfide (B), use a differential scanning calorimeter to raise the temperature from 40 ° C to 340 ° C at 20 ° C / min, and then lower the temperature from 340 ° C to 40 ° C at 20 ° C / min. The peak of the temperature-decreasing crystallization peak is defined as the temperature-decreasing crystallization temperature.
  • the method for lowering the temperature-decreasing crystallization temperature of polyphenylene sulfide (B) to 190 ° C. or lower is not particularly limited, but a method for copolymerizing metaphenylene sulfide and / or orthophenylene sulfide with polyphenylene sulfide mainly formed of a paraphenylene sulfide skeleton. , A method of block-copolymerizing another polymer at the terminal of polyphenylene sulfide, a method of reducing molecular motility by oxidatively cross-linking polyphenylene sulfide, and the like.
  • the difference between the melting point of polyphenylene sulfide (B) and the temperature-decreasing crystallization temperature is preferably 80 ° C. or higher. More preferably, it is 90 ° C. or higher.
  • the difference between the melting point and the temperature-decreasing crystallization temperature refers to the temperature until the resin, which was in a molten state under the temperature-decreasing temperature, crystallizes and solidifies. Therefore, if the difference between the melting point and the temperature-decreasing crystallization temperature is large, it means that the solidification of the resin is delayed.
  • the difference between the melting point of the polyphenylene sulfide (B) and the temperature-decreasing crystallization temperature is 80 ° C.
  • the upper limit of the difference between the melting point of the polyphenylene sulfide (B) and the temperature-decreasing crystallization temperature is preferably 120 ° C.
  • the method for increasing the difference between the melting point of the polyphenylene sulfide (B) and the temperature-decreasing crystallization temperature to 80 ° C. or higher is not particularly limited, but metaphenylene sulfide and / or orthophenylene sulfide is mainly added to the polyphenylene sulfide formed by the paraphenylene sulfide skeleton. Examples thereof include a method of copolymerizing, a method of blocking copolymerizing another polymer at the end of polyphenylene sulfide, and a method of reducing molecular motility by oxidatively cross-linking polyphenylene sulfide.
  • the polyphenylene sulfide (B) preferably contains homopolyphenylene sulfide composed of only paraphenylene sulfide units and copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units.
  • homopolyphenylene sulfide and copolymerized polyphenylene sulfide By containing homopolyphenylene sulfide and copolymerized polyphenylene sulfide, the crystallinity of polyphenylene sulfide can be increased while reducing the amount of gas generated during molding, and the surface smoothness and mechanical properties, fluidity and molding cycleability can be improved. Achieving more compatibility.
  • the content of polyphenylene sulfide (B) is preferably 30% by mass or more and 98.9% by mass or less, more preferably 40% by mass or more and 94.5% by mass, based on the total amount (100% by mass) of the molding material. It is mass% or less, more preferably 50% by mass or more, and 89% by mass or less. By adjusting to such a range, a molding material having excellent moldability and handleability can be obtained. In addition, excellent mechanical properties can be imparted to the molded product.
  • the content of polyphenylene sulfide (B) is less than 30% by mass, the amount of polyphenylene sulfide resin (B) contained in the molding material is small, so that the reinforcing fiber bundle (A) and the polyphenylene sulfide resin (B) are used during molding. May not be sufficiently melt-kneaded or the fluidity may decrease during injection molding. In that case, the reinforcing fiber bundle (A) cannot be sufficiently dispersed in the molded product, which makes molding difficult and may not be preferable.
  • the content of polyphenylene sulfide (B) exceeds 98.9% by mass, the amount of the reinforcing fiber bundle (A) contained in the molding material is relatively small, so that the polyphenylene sulfide (B) is imparted to the molded product. Since the fiber reinforcing effect becomes insufficient, the mechanical properties of the obtained molded product become insufficient, which may be unfavorable. Further, in the case where the polyphenylene sulfide (B) covers a part or all of the periphery of the strand-shaped composite in the molding material, and the polyphenylene sulfide (B) is less than 30% by mass, it is the case. Since the amount of polyphenylene sulfide (B) is small, the coating layer becomes thin, the molding material is easily cracked, and the handleability is deteriorated, which may be unfavorable.
  • the molecular weight of polyphenylene sulfide (B) is preferably 10,000 or more, more preferably 20,000 or more, and particularly particularly, from the viewpoint of the mechanical properties of the molded product obtained by molding the molding material. It is preferably 30,000 or more. This is advantageous from the viewpoint that the larger the weight average molecular weight, the higher the strength and elongation of the matrix resin.
  • the upper limit of the weight average molecular weight is not particularly limited, but is preferably 1,000,000 or less, and more preferably 500,000 or less, from the viewpoint of fluidity during molding.
  • the weight average molecular weight can be determined by using a general GPC (gel permeation chromatography) such as the SEC (size exclusion chromatography).
  • polyphenylene sulfide (B) includes mica, talc, kaolin, hydrotalcite, sericite, bentonite, zonotrite, sepiolite, smectite, montmorillonite, wallastenite, silica, calcium carbonate, glass beads, and glass depending on the application.
  • Flame retardants such as ammonium polyphosphate, aromatic phosphate and red phosphorus, organic acid metal salt flame retardants such as boric acid metal salts, carboxylate metal salts and aromatic sulfonimide metal salts, zinc borate, Inorganic flame retardants such as zinc, zinc oxide and zirconium compounds, nitrogen flame retardants such as cyanuric acid, isocyanuric acid, melamine, melamine cyanurate, melamine phosphate and nitrogenated guanidine, fluoroflame retardants such as PTFE, polyorganosiloxane Silicone flame retardants such as, metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide, and other flame retardants, cadmium oxide, zinc oxide, ferrous oxide, ferric oxide, ferrous oxide.
  • organic acid metal salt flame retardants such as boric acid metal salts, carboxylate metal salts and aromatic sulfonimide metal salts, zinc borate
  • Inorganic flame retardants such as zinc, zinc oxide
  • Flame retardants such as ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and titanium oxide, pigments, dyes, lubricants, mold retardants, compatibilizers, dispersants, mica, talc and kaolin etc.
  • Crystal nucleating agents, plasticizing agents such as phosphate esters, heat stabilizers, antioxidants, anticoloring agents, UV absorbers, fluidity modifiers, foaming agents, antibacterial agents, anti-vibration agents, deodorants, sliding A sex modifier, an antistatic agent such as polyether ester amide, or the like may be added.
  • the resin (C) (impregnated resin) is preferably one or more resins selected from the group consisting of epoxy resins, phenol resins, and terpene resins.
  • the dispersibility of the reinforcing fiber can be improved when the molding material is molded.
  • the impregnated resin has a lower melt viscosity than polyphenylene sulfide (B). Since the melt viscosity of the impregnated resin is lower than that of polyphenylene sulfide (B), the fluidity of the impregnated resin is high when the molding material is molded, and the effect of dispersing the reinforcing fiber bundle in the polyphenylene sulfide (B) is further improved. be able to.
  • the melt viscosity of the impregnating resin can be made lower than that of polyphenylene sulfide (B), and the molded product can be molded. Since the dispersibility of the reinforcing fiber bundle in the above can be improved, the surface smoothness can be improved while improving the mechanical properties of the molded product obtained by molding the molding material of the present invention, which is preferable.
  • the impregnated resin preferably has a high affinity with polyphenylene sulfide (B).
  • B polyphenylene sulfide
  • the melt viscosity of the impregnated resin at 200 ° C. is preferably 0.01 to 10 Pa ⁇ s.
  • the melt viscosity is more preferably 0.05 Pa ⁇ s or more, and further preferably 0.1 Pa ⁇ s or more.
  • the melt viscosity at 200 ° C. is 10 Pa ⁇ s or less, the impregnated resin can be easily impregnated into the inside of the reinforcing fiber bundle (A).
  • the melt viscosity is preferably 5 Pa ⁇ s or less, and more preferably 2 Pa ⁇ s or less.
  • the melt viscosity of the impregnated resin at 200 ° C. can be measured by a viscoelasticity measuring instrument at 0.5 Hz using a 40 mm parallel plate.
  • the number average molecular weight of the impregnated resin is preferably 200 to 5,000. When the number average molecular weight is 200 or more, the bending strength and the tensile strength of the molded product can be further improved.
  • the number average molecular weight is more preferably 1,000 or more. Further, when the number average molecular weight is 5,000 or less, the viscosity of the impregnated resin is moderately low, so that the impregnation property into the reinforcing fiber bundle (A) is excellent, and the dispersibility of the reinforcing fibers in the molded product is further improved. Can be made to.
  • the number average molecular weight is more preferably 3,000 or less.
  • the number average molecular weight of the impregnated resin can be measured by gel permeation chromatography (GPC).
  • the impregnated resin preferably has a heating weight loss of 5% by weight or less when heated in nitrogen at 280 ° C. for 30 minutes. More preferably, it is 3% by weight or less.
  • the heating weight loss is 5% by weight or less, it is possible to suppress the generation of decomposition gas when the reinforcing fiber bundle (A) is impregnated, and it is possible to suppress the generation of voids and the poor surface appearance during molding. ..
  • the generated gas can be suppressed especially in molding at a high temperature.
  • the weight loss by heating in the present invention represents the weight loss rate of the impregnated resin before and after heating under the heating conditions, where the weight of the impregnated resin before heating is 100%, and can be obtained by the following formula.
  • the weight before and after heating can be determined by measuring the weight at the molding temperature by thermogravimetric analysis (TGA) in an air atmosphere at a heating rate of 10 ° C./min using a platinum sample pan. can.
  • TGA thermogravimetric analysis
  • [Weight%] ⁇ (Weight before heating-Weight after heating) / Weight before heating ⁇ x 100
  • the epoxy resin preferably used as the impregnating resin is a compound having two or more epoxy groups, which does not substantially contain a curing agent, and even when heated, it is subjected to so-called three-dimensional crosslinking. A compound that does not cure. Since the epoxy resin has an epoxy group, it easily interacts with the reinforcing fibers, and at the time of impregnation, it easily adapts to the reinforcing fiber bundle (A) and is easily impregnated. In addition, the dispersibility of the reinforcing fibers during the molding process is further improved.
  • examples of the epoxy resin include glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and alicyclic epoxy resin. Two or more of these may be used.
  • examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, and hydrogenated bisphenol.
  • Examples of the glycidyl ester type epoxy resin include hexahydrophthalic acid glycidyl ester and dimer acid diglycidyl ester.
  • Examples of the glycidylamine type epoxy resin include triglycidyl isocyanurate, tetraglycidyldiaminodiphenylmethane, tetraglycidylmethylenediamine, and an aminophenol type epoxy resin.
  • Examples of the alicyclic epoxy resin include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate and 3,4-epoxycyclohexylmethylcarboxylate.
  • the glycidyl ether type epoxy resin is preferable, and the bisphenol A type epoxy resin and the bisphenol F type epoxy resin are more preferable because the balance between the viscosity and the heat resistance is excellent.
  • the phenol resin is a resin having a phenol skeleton, may have a substituent, and may be cresol or naphthol.
  • Specific examples of the phenol resin include phenol novolac resin, o-cresol novolak resin, phenol aralkyl resin, naphthol novolak resin, naphthol aralkyl resin and the like.
  • o-cresol novolak resin is preferably used because it has an excellent balance between heat resistance and handleability such as melt viscosity, so that the take-up speed of the complex can be increased and the flame retardancy can be maintained higher. ..
  • the melting point of the phenol resin is not particularly limited, but it is preferably higher than 80 ° C. from the viewpoint of improving the heat resistance and handleability of the molding material and suppressing bleeding out during long-term storage of the molding material. More preferably, it exceeds 100 ° C., and even more preferably 120 ° C.
  • the upper limit of the melting point is not particularly limited, but the melting point of the phenol resin can be obtained from the DSC measurement. Specifically, it can be obtained from the value of the endothermic peak top measured under the condition of a temperature rise of 40 ° C./min.
  • the terpene resin may be a resin made of a polymer obtained by polymerizing a terpene monomer alone in the presence of a Friedelcraft type catalyst in an organic solvent, a terpene monomer and an aromatic monomer, or the like. Examples thereof include a resin made of a polymer obtained by copolymerizing with.
  • terpene monomers include ⁇ -pinene, ⁇ -pinene, dipentene, d-lymonen, milsen, aloocimen, osimene, ⁇ -ferandren, ⁇ -terpinene, ⁇ -terpinene, terpineolene, 1,8-cineole, 1, Examples thereof include monoterpene monoterpenes such as 4-cineole, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, sabinen, paramentadiens and curenes. Moreover, styrene, ⁇ -methylstyrene and the like are mentioned as an aromatic monomer.
  • ⁇ -pinene, ⁇ -pinene, dipentene, and d-limonene are preferable from the viewpoint of compatibility, and a homopolymer of the compound is more preferable. Further, a hydrogenated terpene resin obtained by hydrogenating the terpene resin is more preferable from the viewpoint of compatibility.
  • a terpene resin obtained by reacting a terpene monomer and phenols in the presence of a catalyst can also be used.
  • the phenols those having 1 to 3 substituents of at least one selected from the group consisting of an alkyl group, a halogen atom and a hydroxyl group on the benzene ring of phenol are preferably used. Specific examples thereof include cresol, xylenol, ethylphenol, butylphenol, t-butylphenol, nonylphenol, 3,4,5-trimethylphenol, chlorophenol, bromophenol, chlorocresol, hydroquinone, resorcinol, orcinol and the like. Two or more of these may be used. Of these, phenol and cresol are preferred.
  • the number average molecular weight of the terpene resin or the terpene phenol resin is preferably 100 to 5,000. More preferably, it is 500 to 1,000.
  • the number average molecular weight is 100 or more, the heat loss of the terpene resin is lowered, and the dispersibility of the reinforcing fiber bundle (A) in the molded product is improved, which is preferable.
  • the number average molecular weight is 5,000 or less, the viscosity of the terpene resin is lowered, so that the impregnation property into the reinforcing fiber bundle (A) and the fiber dispersibility during molding are improved, which is preferable.
  • the content of the resin (C) is preferably 0.1% by mass or more and 20% by mass or less, more preferably 3% by mass or more, based on the total amount (100% by mass) of the molding material. It is 10% by mass or less. Within such a range, a molding material having excellent moldability and handleability can be obtained. If the content of the impregnated resin is less than 0.1% by weight, the impregnated fiber bundle (A) may be insufficiently impregnated, and the handleability of the obtained molding material may be insufficient, which is not preferable. On the other hand, if it exceeds 20% by mass, the amount of low molecular weight components contained in the molded product is relatively large, which is not preferable because the molded product becomes brittle and the mechanical properties deteriorate.
  • the molding material of the present invention is kneaded by, for example, injection molding to become a final molded product.
  • the handleability of the molded material can be improved, and as a result, the variation in the mechanical properties of the molded product can be suppressed and the surface smoothness of the molded product can be suppressed. It is possible to improve the fluidity, suppress the decrease in the fluidity of the molding material, and improve the fluidity. In addition, excellent mechanical properties can be imparted to the obtained molded product.
  • the molding material of the present invention is further enhanced to contain 0.1 to 10% by mass of a compound having two or more compounds having at least one structure selected from a carbodiimide structure, a urea structure and a urethane structure in one molecule. It is preferable from the viewpoint of further enhancing the affinity between the fiber bundle (A) and the polyphenylene sulfide (B) and improving the tensile properties of the obtained molded product.
  • the blending amount is preferably 0.3 to 8% by mass, and is particularly preferably in the range of 0.5 to 5% by mass from the viewpoint of generating decomposition gas during kneading with the matrix resin.
  • the compound having a carbodiimide structure that is, the carbodiimide compound includes polycarbodiimide, and examples thereof include aliphatic polycarbodiimide and aromatic polycarbodiimide, and the affinity and reactivity between the reinforcing fiber bundle (A) and polyphenylene sulfide (B). From the viewpoint of the above, aliphatic polycarbodiimide is preferably used.
  • the repeating unit represented by (indicating the divalent organic group of the aliphatic compound) is the main constituent unit, preferably the repeating unit is 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol. It is a homopolymer or copolymer containing% or more.
  • a compound obtained by reacting diisocyanate with a diamine containing a compound containing a plurality of amino groups for example, hydrazine, dihydrazide, etc.
  • polyurea can be synthesized by reacting isocyanate with water to form unstable carbamic acid. Carbamic acid decomposes to generate carbon dioxide and immediately reacts with excess isocyanate to form amino groups that form urea crosslinks.
  • it can also be obtained by treating a compound having a carbodiimide structure with water to react the carbodiimide with urea.
  • a compound obtained by reacting bischloroformate with a diamine can be used.
  • polyurethane can be synthesized by reacting the diisocyanate with a diol such as macroglycol, a polyol, or a combination of macroglycol and a single chain glycol extender.
  • polycarbodiimide is preferably used from the viewpoint of interfacial adhesion with the reinforcing fiber bundle (A).
  • the molded product of the present invention is a molded product containing reinforcing fibers and polyphenylene sulfide, and the weight average fiber length of the reinforcing fibers is 0.3 mm or more and 3.0 mm or less, and the melting point of the polyphenylene sulfide is 270 ° C. or less. It is a molded product. Further, the molded product of the present invention is a molded product containing a reinforcing fiber and polyphenylene sulfide (B), and the weight average fiber length of the reinforcing fiber is 0.3 mm or more and 3.0 mm or less, and the polyphenylene sulfide is used. It is a molded product having a temperature-decreasing crystallizing temperature of 190 ° C. or lower.
  • the weight average fiber length of the reinforcing fibers contained in the molded product is 0.3 to 3.0 mm. More preferably, it is 0.5 to 2.8 mm. More preferably, it is 0.8 to 2.5 mm.
  • the weight average fiber length of the reinforcing fiber is 0.3 to 3.0 mm or more, the mechanical properties of the molded product can be sufficiently exhibited.
  • the weight average fiber length of the reinforcing fiber exceeds 3.0 mm, the fiber pattern of the reinforcing fiber tends to remarkably appear on the surface of the molded product, and waviness derived from the reinforcing fiber occurs on the surface of the molded product, resulting in poor appearance. It may not be preferable because it invites you. Therefore, by setting the weight average fiber length of the reinforcing fiber to 3.0 mm or less, such waviness can be suppressed and the surface appearance of the molded product can be improved.
  • the type of the reinforcing fiber is not particularly limited, and the reinforcing fiber described in the description of the reinforcing fiber bundle of the molding material can be exemplified. Further, the types and combinations of preferable reinforcing fibers are the same, and the reasons for the preferred are the same.
  • the reinforcing fiber is 1 to 50% by mass with respect to 100% by mass of the molded product. More preferably, it is 10 to 30% by mass. If the content of the reinforcing fiber is less than 1% by mass, the mechanical properties of the obtained molded product may be insufficient, and if it exceeds 50% by mass, the appearance of the molded product may be poor.
  • a sizing agent is attached to the reinforcing fiber.
  • the type of the sizing agent is not particularly limited, but one or more kinds of sizing agents such as epoxy resin, urethane resin, acrylic resin and various thermoplastic resins can be used in combination.
  • the polyphenylene sulfide resin contained in the molded product in the present invention preferably has a melting point of 270 ° C. or lower. By setting the melting point to 270 ° C. or lower, molding can be performed at a lower molding temperature than the conventional polyphenylene sulfide resin. This makes it possible to suppress the thermal decomposition of the impregnated resin, the sizing agent and other additives contained in the molding material, that is, the generated gas.
  • the melting point of polyphenylene sulfide (B) is more preferably 260 ° C. or lower. Further, from the viewpoint of heat resistance, the melting point of polyphenylene sulfide (B) is preferably 240 ° C. or higher.
  • the polyphenylene sulfide resin contained in the molded product in the present invention preferably contains homopolyphenylene sulfide composed of only paraphenylene sulfide units and copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units.
  • homopolyphenylene sulfide and the copolymerized polyphenylene sulfide By using the homopolyphenylene sulfide and the copolymerized polyphenylene sulfide, the crystallization rate and the temperature-decreasing crystallization temperature can be appropriately controlled.
  • the solidification rate of the molded product can be controlled, for example, sudden solidification in the mold during injection molding and extreme solidification delay can be suppressed, and as a result, the fluidity of the resin during molding can be improved. Can be secured. In addition, the cycle time can be maintained.
  • the degree of crystallization of the polyphenylene sulfide resin is controlled by the above-mentioned polyphenylene sulfide resin containing homopolyphenylene sulfide composed of only paraphenylene sulfide units and copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units. can do. Since the crystallinity of the polyphenylene sulfide resin can be increased by appropriately adjusting the blending amount of the polyphenylene sulfide resin described above, for example, the crystallinity of the polyphenylene sulfide resin in the molded product obtained by injection molding. Can be increased and mechanical properties can be improved.
  • the polyphenylene sulfide resin may contain homopolyphenylene sulfide composed of only paraphenylene sulfide units and copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units.
  • a homopolyphenylene sulfide pellet consisting of only paraphenylene sulfide units and a copolymerized polyphenylene sulfide pellet consisting of paraphenylene sulfide units and metaphenylene sulfide units are dry-blended to obtain pellets in which both are mixed (hereinafter referred to as mixed pellets) in advance.
  • homopolyphenylene sulfide consisting of only paraphenylene sulfide units and copolymerized polyphenylene sulfide consisting of paraphenylene sulfide units and metaphenylene sulfide units can be obtained. It may be mixed.
  • the blending ratio of the homopolyphenylene sulfide consisting of only the paraphenylene sulfide unit and the copolymerized polyphenylene sulfide consisting of the paraphenylene sulfide unit and the metaphenylene sulfide unit is not particularly limited, but the homopolyphenylene sulfide consisting only of the paraphenylene sulfide unit and Homopolyphenylene sulfide consisting only of paraphenylene sulfide units is 1 to 50 parts by weight, and paraphenylene sulfide units and metaphenylene A compounding ratio of 99 to 50 parts by weight of the copolymerized polyphenylene sulfide consisting of sulfide units is preferable, and more preferably, 5 to 40 parts by weight of homopolyphenylene sulfide consisting only of paraphenylene sulfide units, and paraphenylene sulfide units and meta.
  • the amount of homopolyphenylene sulfide composed of only paraphenylene sulfide units is less than 1 part by weight, the crystallization rate and the temperature-decreasing crystallization temperature cannot be appropriately controlled, and the solidification rate of the molded product becomes extremely slow. Therefore, it may not be preferable because the cycle time during injection molding described above becomes long, and if it exceeds 50 parts by weight, the crystallization speed becomes too fast, so that solidification in the mold during injection molding described above may occur. It may not be preferable because the speed increases and the fluidity decreases.
  • the blending amount of the copolymerized polyphenylene sulfide composed of the paraphenylene sulfide unit and the metaphenylene sulfide unit is less than 50 parts by weight, the crystallization rate becomes too fast, and therefore, in the above-mentioned injection molding, in the mold. It may not be preferable because the solidification rate becomes high and the fluidity decreases, and if it exceeds 99 parts by weight, the crystallization rate and the temperature-decreasing crystallization temperature cannot be appropriately controlled, and the solidification rate of the molded product becomes high. Since it becomes extremely slow, the cycle time at the time of injection molding described above becomes long, which may be unfavorable.
  • the melting point and temperature-decreasing crystallization temperature of polyphenylene sulfide (B) are measured as follows using a differential scanning calorimeter TA3000 (manufactured by Meterer). rice field. [1] Using a differential scanning calorimeter TA3000 (manufactured by Metler), the temperature of the sample was raised from 40 ° C. to 340 ° C. at a heating rate of 20 ° C./min. [2] After raising the temperature in [1], the temperature of the sample was lowered from 340 ° C. to 40 ° C.
  • Weight average fiber length ⁇ (Mi 2 x Ni) / ⁇ (Mi x Ni) Mi: Fiber length (mm) Ni: Number of carbon fibers with fiber length Mi i: Number of measured fibers.
  • the obtained cake, 11880 g of ion-exchanged water, and 4 g of calcium acetate monohydrate (Sigma Aldrich) were placed in an autoclave equipped with a stirrer, the inside of the autoclave was replaced with nitrogen, the temperature was raised to 192 ° C, and the temperature was maintained for 30 minutes. .. After that, the autoclave was cooled and the contents were taken out.
  • the polymer was washed with hexane at 50 ° C. for 15 minutes and filtered twice, and further washed with methanol at 50 ° C. for 15 minutes and filtered twice at 70 ° C. It was washed with water for 15 minutes and filtered once to obtain polyphenylene sulfide (B-5).
  • A-1 Carbon fiber "Trading Card” T800-24K (manufactured by Toray Industries, Inc.) was used.
  • As a carbon fiber sizing agent polyglycerol polyglycidyl ether (epoxy equivalent: 140 g / eq) was attached in an amount of 1.0% by mass based on the total amount of the sizing agent and carbon fibers (100% by mass).
  • A-2) Carbon fiber "Trading Card” M55JB-6K (manufactured by Toray Industries, Inc.) was used.
  • polyglycerol polyglycidyl ether (epoxy equivalent: 140 g / eq) was attached in an amount of 1.5% by mass based on the total amount of the sizing agent and carbon fibers (100% by mass).
  • Example 1 An epoxy resin (jER828 manufactured by Japan Epoxy Resin Co., Ltd.), which is an impregnating resin, was melted in a melting bath at 200 ° C. and supplied to a kiss coater by a gear pump. An epoxy resin was applied from a kiss coater onto a roll heated to 200 ° C. to form a film. The carbon fibers (A-1) were passed through the roll while being in contact with each other, and a certain amount of epoxy resin was adhered to each unit length of the carbon fiber bundle. The carbon fibers to which the epoxy resin was attached were passed between free rolls heated to 230 ° C. and arranged alternately up and down in a straight line to obtain a composite in which the carbon fibers were sufficiently impregnated with the epoxy resin.
  • jER828 manufactured by Japan Epoxy Resin Co., Ltd. which is an impregnating resin
  • polyphenylene sulfide (B-2) was melted in an extruder at 320 ° C. and extruded into a crosshead die attached to the tip of the extruder, and at the same time, the obtained complex was continuously inserted into the crosshead die.
  • the complex was coated with polyphenylene sulfide (B-2) to obtain strands.
  • the obtained strands After cooling the obtained strands, they were cut to a length of 7 mm with a cutter to obtain long fiber pellets, which is the molding material of the present invention.
  • This pellet had a core-sheath structure with a complex as a core and polyphenylene sulfide (B-2) as a sheath.
  • B-2 polyphenylene sulfide
  • the carbon fiber bundles were arranged in parallel in parallel with the axial direction of the molding material, and the length of the carbon fiber bundle was substantially the same as the length of the molding material.
  • the obtained long fiber pellets showed good handleability without fluffing due to transportation.
  • the obtained long fiber pellet-shaped molding material was injected with an injection time of 2 seconds, a back pressure of 10 MPa, a holding pressure time of 10 seconds, and a cycle time of 55.
  • An ISO type tensile dumbbell test piece (molded product) was produced by injection molding under the conditions of seconds, cylinder temperature: 280 ° C., and mold temperature: 160 ° C.
  • the cylinder temperature indicates the temperature of a portion where the molding material of the injection molding machine is heated and melted
  • the mold temperature indicates the temperature of the mold for injecting the molding material into a predetermined shape.
  • the cycle time indicates the time from the start of one injection molding process to the removal of the molded product.
  • the injection pressure here indicates a value obtained by measuring the maximum pressure generated when the molding material melted during injection molding is filled into the mold. The obtained test piece (molded product) was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated by the above-mentioned method. Table 1 shows the characteristics of the molding material, the value of the injection pressure during injection molding, and the evaluation results of the molded product.
  • Example 1 except that the type and content of the reinforcing fiber bundle (A), the type and content of polyphenylene sulfide (B), and the type and content of the resin (C) were changed as shown in Table 1.
  • a molding material long fiber pellet was obtained in the same manner as above.
  • the obtained pellet had a complex in which the epoxy resin was sufficiently impregnated into the carbon fiber.
  • the complex was coated with polyphenylene sulfide.
  • the obtained pellet had a core-sheath structure with a complex as a core and polyphenylene sulfide as a sheath.
  • the length of the obtained long fiber pellet was 7 mm as in Example 1. Further, the carbon fiber bundles were arranged in parallel in parallel with the axial direction of the molding material, and the length of the carbon fiber bundle was substantially the same as the length of the molding material.
  • the long fiber pellets obtained in Examples 2 to 8 and 11 to 14 showed good handleability without fluffing due to transportation.
  • the long fiber pellet obtained in Example 15 contains a large amount of the reinforcing fiber bundle (A), the amount of polyphenylene sulfide (B) contained is relatively small, and uneven coating and fluffing occur. It was seen and the result was inferior in handleability.
  • a molded product was produced and evaluated by injection molding the obtained molding material in the same manner as in Example 1. Table 1 shows the characteristics of the molding material, the value of the injection pressure during injection molding, and the evaluation results of the molded product.
  • Epoxy resin (jER828 manufactured by Japan Epoxy Resin Co., Ltd.), which is an impregnated resin, was melted in a melting bath at 200 ° C. and supplied to a kiss coater by a gear pump in the same manner as in Example 1.
  • An epoxy resin was applied from a kiss coater onto a roll heated to 200 ° C. to form a film.
  • the carbon fibers (A-1) were passed through the roll while being in contact with each other, and a certain amount of epoxy resin was adhered to each unit length of the carbon fiber bundle.
  • the carbon fibers to which the epoxy resin was attached were passed between free rolls heated to 230 ° C. and arranged alternately up and down in a straight line to obtain a composite in which the carbon fibers were sufficiently impregnated with the epoxy resin.
  • the obtained mixed pellets were used in a JSW TEX-30 ⁇ twin-screw extruder (screw diameter 30 mm, die diameter 5 mm, barrel temperature 260 ° C., screw rotation speed 150 rpm), and the mixture was used as the main hopper of the extruder. It was supplied from the above, melt-kneaded, and discharged into a die in a molten state, and the periphery of the composite was covered (by the discharged material) to obtain a molten continuous molding material (strand).
  • the contents of the reinforcing fiber bundle (A), the polyphenylene sulfide resin (B), the resin (C) and the aliphatic polycarbodiimide in the molding material are shown in Table 1 with respect to the molding material (100 parts by mass).
  • the discharge amount in the die was adjusted so as to have the value described.
  • the obtained continuous molding material (strand) was cooled and then cut with a cutter to obtain a molding material (long fiber pellet) having a length of 7 mm.
  • the obtained pellet had a complex in which epoxy was sufficiently impregnated into carbon fibers. Further, in the obtained pellet, the complex has a resin composition composed of polyphenylene sulfide (B-1), polyphenylene sulfide (B-2) and an aliphatic polycarbodiimide (“Carbodilite HMV-8CA” (manufactured by Nisshinbo Chemical Co., Ltd.)). It was covered with things. Further, the obtained pellet had a core-sheath structure in which the composite was used as the core and the resin composition described above was used as the sheath. The length of the obtained long fiber pellet was 7 mm as in Example 1. Further, the carbon fiber bundles were arranged in parallel in parallel with the axial direction of the molding material, and the length of the carbon fiber bundle was substantially the same as the length of the molding material.
  • the obtained long fiber pellets showed good handleability without fluffing due to transportation.
  • a molded product was produced and evaluated by injection molding the obtained molding material in the same manner as in Example 1. Table 1 shows the characteristics of the molding material, the value of the injection pressure during injection molding, and the evaluation results of the molded product.
  • Example 1 (Comparative Examples 1 to 4) Example 1 except that the type and content of the reinforcing fiber bundle (A), the type and content of polyphenylene sulfide (B), and the type and content of the resin (C) were changed as shown in Table 1.
  • a molding material (long fiber pellet) was obtained in the same manner as above.
  • the obtained pellet had a complex in which the epoxy resin was sufficiently impregnated into the carbon fiber.
  • the complex was coated with polyphenylene sulfide.
  • the obtained pellet had a core-sheath structure with a complex as a core and polyphenylene sulfide as a sheath.
  • the length of the obtained long fiber pellet was 7 mm as in Example 1. Further, the carbon fiber bundles were arranged in parallel in parallel with the axial direction of the molding material, and the length of the carbon fiber bundle was substantially the same as the length of the molding material.
  • thermoplastic resin composition having a length of 7 mm.
  • the obtained pellets did not contain the reinforcing fiber bundle (A), the length of the reinforcing fiber bundle could not be measured, and the core-sheath structure was not provided.
  • the obtained resin pellets were injected with an injection time of 2 seconds, a back pressure of 10 MPa, a holding pressure time of 10 seconds, a cycle time of 45 seconds, and a cylinder temperature:
  • An ISO type tensile dumbbell test piece (molded product) was produced by injection molding under the conditions of 280 ° C. and mold temperature: 160 ° C.
  • the cylinder temperature indicates the temperature of a portion where the molding material of the injection molding machine is heated and melted
  • the mold temperature indicates the temperature of the mold for injecting the molding material into a predetermined shape.
  • the obtained test piece (molded product) was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated by the above-mentioned method. The evaluation results are shown in Table 2.
  • Examples 2 to 4, 6 to 10, 12 to 15 include homopolyphenylene sulfide composed of only paraphenylene sulfide units and copolymerized polyphenylene sulfide composed of paraphenylene sulfide units and metaphenylene sulfide units. Therefore, as compared with the case where only the copolymerized polyphenylene sulfide composed of metaphenylene sulfide units is contained (Examples 1 and 5), the crystallization rate, that is, the solidification rate is increased, but the molding material in a molten state in the mold is used. The filling of the molding material into the mold could be completed before the solidification of the material began. As described above, the molding materials of Examples 2 to 4, 6 to 10, and 12 to 15 were able to further shorten the cycle time.
  • the molding temperature can be lowered as compared with the case where the melting point of polyphenylene sulfide is lowered by copolymerizing polysiloxane (Example 11), so that the gas can be used.
  • the generation could be further suppressed, and the surface roughness of the molded product could be further reduced.
  • Example 15 since the contents of the carbon fiber bundles in Examples 1 to 14 were in a suitable range, the injection pressure could be further lowered as compared with Example 15.
  • Comparative Examples 1 to 4 were molding materials having a melting point of polyphenylene sulfide higher than 270 ° C. and inferior in surface smoothness of the molded product after molding due to gas generation derived from the sizing agent for the reinforcing fiber bundle during molding.
  • Comparative Example 5 was a molding material having inferior mechanical properties because it did not contain the reinforcing fiber bundle (A).

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